Interpreting Vibrational Sum-frequency Spectra of Sulfur Dioxide at the Air/Water Interface: A Comprehensive Molecular Dynamics Study
We investigated the solvation and spectroscopic properties of SO2 at the air/water interface using molecular simulation techniques. Molecular interactions from both Kohn-Sham (KS) density functional theory (DFT) and classical polarizable models were utilized to understand the properties of SO2:(H2O)x complexes in the vicinity of the air/water interface. The KS-DFT was included to allow comparisons with sum-frequency generation spectroscopy through the identification of surface SO2:(H2O)x complexes. Using our simulation results, we were able to develop a much more detailed picture for the surface structure of SO2 that is consistent with the spectroscopic data obtained Richmond and coworkers (J. Am. Chem. Soc. 127, 16806 (2005)). We also found many similarities and differences between to the two interaction potentials, including a noticeable weakness of the classical potential model in reproducing the asymmetric hydrogen bonding of water with SO2 due to its inability to account for SO2 resonance structures. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.
- Research Organization:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 982542
- Report Number(s):
- PNNL-SA-70346; KC0301020; TRN: US201014%%369
- Journal Information:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 114, Issue 21; ISSN 1520-6106
- Country of Publication:
- United States
- Language:
- English
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